AU2011244846B2 - Resin bonded sorbent - Google Patents

Resin bonded sorbent Download PDF

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AU2011244846B2
AU2011244846B2 AU2011244846A AU2011244846A AU2011244846B2 AU 2011244846 B2 AU2011244846 B2 AU 2011244846B2 AU 2011244846 A AU2011244846 A AU 2011244846A AU 2011244846 A AU2011244846 A AU 2011244846A AU 2011244846 B2 AU2011244846 B2 AU 2011244846B2
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molecular sieve
nylon
sorbent
resin
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Samual A. Incorvia
Thomas Powers
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Multisorb Technologies Inc
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Multisorb Technologies Inc
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Abstract

Abstract The invention relates to improved resin bonded sorbent compositions and articles of manufacture fabricated therewith, such as air conditioning and refrigeration components. The introduction of desiccants into resinous molding compositions s enables the elimination of more conventional bagged desiccant containments. The novel molding compositions of the invention and parts fabricated therewith are multi functional, beneficially combining structural, mechanical and adsorptive capabilities without requiring the usual reinforcing additives. Consequently, with the omission of reinforcing additives the novel molding compositions of the invention are further 10 characterized by higher moisture adsorptive capacities by allowing for higher sorbent loading factors than prior adsorbent-containing molding compositions. Fig. 1. 2918958_1 (GHMatters) P75921 AU.1 28/10/11 WO 2006/078855 PCTIUS2006/001957 |C| CU-

Description

GRIFFITH HACK PATENTS, TRADE MARKS, IP LAW SPECIFICATION OF PATENT APPLICATION COUNTRY AUSTRALIA TYPE Divisional Patent DATE 20 January 2006 TITLE RESIN BONDED SORBENT APPLICANTS) MULTISORB TECHNOLOGIES, INC.
AUSTRALIA Patents Act 1990 COMPLETE SPECIFICATION Standard Patent Applicant (): MULTISORB TECHNOLOGIES, INC. Invention Title: RESIN BONDED SORBENT The following statement is a full description of this invention, including the best method for performing it known to me/us: RESIN BONDED SORBENT FIELD OF THE INVENTION 5 [00011 The present invention relates generally to molding compositions, and more particularly, to improved injection molding compositions and articles of manufacture fabricated therefrom comprising water adsorbing additives in a resinous base. 10 BACKGROUND OF INVENTION [0002] Incorporation of sorbents or desiccants into resin matrices has been revealed in several contexts. Formation of these resins into structural or functional shapes by various processes has been described in certain applications. Similarly, fillers have been added to structural molding resins. Low cost mineral or other fillers 15 have been added to resin-containing compositions to extend the resin and reduce costs, while maintaining strength sufficient for the intended end-use application of the molded article. It is also a frequent practice to add reinforcing materials, such as glass fibers or beads to enhance mechanical properties of molding resins, e.g., hardness, tensile displacement, and so on. With reinforcing additives, just as with fillers, it has 20 been found there are ranges within which the desired effects of extending the resin or reinforcing the molded article are accomplished while maintaining satisfactory injection molding and mechanical properties. [0003] Nevertheless, molding compositions comprising reinforcing additives have not been entirely satisfactory for a number of end-use applications. For example, 25 molding composition having relatively high loading levels of reinforcing additives, such as glass fibers and glass beads have the affect of limiting the loading factor of desiccant additives which may be introduced into such molding compositions for optimal moisture adsorption performance. However, with a corresponding reduction in the loading of reinforcing additives and an increase in the loading of desiccant 30 additives there was also a potential for a reduction in desirable mechanical properties, such as hardness, tensile strength, and other mechanical properties. [0004] Accordingly, there is a need for improved resinous molding compositions, and more particularly, injection molding compositions and articles of 1 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ manufacture made therefrom, wherein the compositions and manufactured articles retain high loading levels of desiccant additives without off-setting desirable mechanical properties of the resins. 5 SUMMARY OF INVENTION [0005] It is therefore desirable if the invention provides improved multifunctional resinous molding compositions with a high level of moisture adsorbing properties without substantial trade-offs in mechanical properties. [0006] A first aspect of the invention provides a molded article formed of a 10 composition comprising from 25 to 55 wt% of a molecular sieve in combination with from 45 to 75 wt% of a thermoplastic nylon, wherein said molecular sieve-nylon combination is present in said composition as a nylon bonded molecular sieve, said molecular sieve comprising a plurality of particles mixed throughout said nylon in a miscible manner. 15 [0006a] An embodiment of the present invention comprises at least a "resin bonded sorbent" composition comprising a resin and a sufficient amount of sorbent to remove moisture from the environment the molded article will be used in. That is to say, one principal aspect of the invention relates to multifunctional molding compositions having at least a moisture adsorbing amount of a sorbent in combination 20 with a resin. The sorbent-resin combination can be present in the composition as a resin bonded sorbent. The molding composition is further characterized by enhanced mechanical properties in the absence of an additive having a utility generally recognized for reinforcing articles of manufacture fabricated from resinous molding compositions. 25 [0006b] In an embodiment, said composition does not comprise a coupling agent or a compatibilizing agent to promote bonding of said nylon and said molecular sieve. [0006c] In an embodiment, said composition comprises a coupling agent or a compatibilizing agent to promote bonding of said nylon and said molecular sieve. 30 2 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ [0006d] In an embodiment, said coupling or compatibilizing agent is a member selected from the group consisting of reactive and nonreactive agents. [0006e] In an embodiment, said reactive agent and non-reactive agent is a member selected from the group consisting of a metal, an acrylate, stearate, block 5 copolymer, maleate, epoxy and a silane. [0006f] In an embodiment, said nylon bonded molecular sieve comprises from 35 to 42 wt% molecular sieve and from 58 to 65 wt% thermoplastic nylon. [0006g] In an embodiment, said composition does not comprise any reinforcing additive other than said molecular sieve. 10 [0006h] In an embodiment, said composition comprises from 5 to 15% of a reinforcing agent in addition to said molecular sieve. [0006i] In an embodiment, said article is a refrigeration or air conditioning cycle component. [0006j] In an embodiment, said component is a member selected from the 15 group consisting of a U-tube assembly; a liner or sleeve; accumulator, plug/filter assembly; integral threaded plug and filter, and accumulator-J-tube and cap. [0006k] In an embodiment, said article is an injection-molded article. [00061] In an embodiment, said composition comprises from 5 to 15% of a reinforcing agent in addition to said sorbent. 20 [0006m] In an embodiment, said molded article has enhanced mechanical properties when in the absence of an additive having a utility generally recognized for reinforcing articles of manufacture fabricated from resinous molding compositions 25 [0007] An embodiment of the invention further relates to multifunctional sorbent-resin molding compositions comprising moisture adsorbing-mechanical property enhancing amounts of adsorbent in combination with reinforcing additives and resin, wherein reduced amounts of reinforcing additives can be employed than otherwise normally required for enhanced mechanical properties. Surprisingly, these 30 inventors discovered that mechanical properties of molding resins can be enhanced 3 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ with the introduction of sorbents/desiccants thereby allowing for the introduction of reduced amounts of further additives specifically intended for enhancing mechanical properties of sorbent modified injection molding resins, such as glass fibers and glass beads. This is believed to be especially significant because with higher loadings of 5 molding compositions with reinforcing agents this can actually have a deleterious or degrading effect on the strength of molded articles fabricated therewith. Accordingly, it is desirable of the invention to provide for sorbent-containing molding compositions wherein the mechanical properties imparted by the adsorbent enables usage of lesser amounts of mechanical strength enhancing additives specifically intended for 10 reinforcing resinous molding compositions. [0008] In particular, the multifunctional molding compositions of the invention may comprise from about 25 to about 55 wt% sorbent, and from about 45 to about 75 wt% resin, usually a thermoplastic material, either homopolymeric type or copolymer having two or more comonomers. A preferred amount of sorbent is in 15 the range from about 35 to about 42 wt%, and more preferably, an amount of about 40 wt%. One representative preferred molecular sieve is a 4A molecular type; however, other sieves may be used selected from both natural and artificial zeolites. [0009] For purposes of this invention the expression "resin bonded sorbent", as appearing in the specification and claims, is intended to mean a surface 20 compatibility occurring between the sorbent and the resin through a loss of crystallinity of the resin, whereby the sorbent becomes wetted and miscible with the resin due to a reduction in surface tension. The expression "resin bonded sorbent" is intended to include binding between the resin and sorbent, which can occur, for example, through heating the sorbent with the resin, or which can be bound through 25 suitable, non-contaminating coupling, surfactant or compatibilizing agents, discussed in greater detail below. [0010] An embodiment of the invention provides molded articles of manufacture fabricated from the resin bonded adsorbent compositions as disclosed herein, and more particularly, to provide molded components, such as refrigeration 30 cycle and air conditioner components made from molding compositions comprising generally from about 25 to about 55 wt% sorbent, and from about 45 to about 75 wt% resin. In the case of most mobile refrigeration systems, due to performance issues, 4 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ often there are preferably no other materials mixed with the resin/sorbent combination, as defined herein. [0011] A method of manufacturing an article according to any preceding claim, comprising of steps of: 5 (i) providing a molding composition comprising from 25 to 55 wt% of a molecular sieve in combination from 45 to 75 wt% of a thermoplastic nylon wherein said molecular sieve-nylon combination is present in said composition as a nylon bonded molecular sieve, said molecular sieve comprising a plurality of particles mixed throughout said nylon in a miscible manner, said molded article having enhanced 10 mechanical properties when in the absence of an additive having a utility generally recognized for reinforcing articles of manufacture fabricated from resinous molding compositions, and (ii) molding said component from said article. 15 [001la] In an embodiment, said step of molding is injection molding. [0011b] An embodiment of the present invention comprises methods for making improved articles of manufacture, such as components for vehicular air conditioning systems which can eliminate the usual desiccant bag, including refrigeration systems 20 comprising the steps of forming a composition comprising at least from about 25 to about 55 wt% sorbent, such as a molecular sieve, e.g., both natural and artificial zeolites, and from about 45 to about 75 wt% resin, and then molding a component from the compositions, such as by injection molding processes. 25 BRIEF DESCRIPTION OF THE DRAWINGS [0012] The figures are for illustration purposes only and are not necessarily drawn to scale. Embodiments of the invention itself, however, both as to organization and method of operation, may best be understood by reference to the detailed description which follows taken in conjunction with the accompanying non-limiting 30 drawings in which: Fig. 1 is an end view of an accumulator in accordance with an embodiment of the present invention; 5 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ Fig. 2 is a partial cross sectional side view of an accumulator in accordance with an embodiment of the present invention; Fig. 3 is an exploded view of a filter/desiccant bag/aluminum fitting component of a refrigeration system in accordance with the prior art; 5 Fig. 4 is a side view of the component of Fig. 3; Fig. 5 is a one-piece filter/fitting made in accordance with the composition of an embodiment of the present invention; Fig. 6 is an illustration of the use of the device shown in Fig. 5 along with a desiccant bag; 10 Fig. 7 shows a cross sectional view of an embodiment of the part shown in Fig. 5 in use atop a condenser; Fig. 8 illustrates a mobile refrigeration accumulator baffle portion of a refrigerant vapor/liquid separator, such as is used in the receive of an automobile air conditioning system, made in accordance with an embodiment of the present 15 invention; and Fig. 9 illustrates a cap portion for the separator of Fig. 8. DETAILED DESCRIPTION OF THE INVENTION [0013] It would be desirable for reasons of cost and productivity to 20 incorporate a sorbent into a resin, and in particular one suitable for injection molding, in such a way that its adsorptive properties are preserved and the molding properties of the resin are maintained without degrading mechanical properties. Surprisingly, the novel molding compositions of the invention and parts fabricated therewith are multi-functional, beneficially combining structural, mechanical and adsorptive 25 capabilities without requiring the usual reinforcing additives. Consequently, with the omission of reinforcing additives the novel molding compositions of embodiments of the invention are further characterized by higher moisture adsorptive capacities by allowing for higher sorbent loading factors than prior adsorbent-containing molding compositions. 6 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ [0014] Serendipitously, it was discovered as a part of the present invention, that sorbents of the "resin bonded sorbent" molding compositions can have the beneficial effect of imparting reinforcement to the molding compositions of the invention while retaining their moisture adsorptive capacity, but without requiring the 5 usual and customary strengthening additives, such as glass beads, glass fiber, and the like. This can allow for higher loading factors of sorbent additives for maximizing adsorptive properties of the molding composition without trade-offs occurring in terms of significantly altered mechanical properties of the molding composition. [0015] While embodiments of the present invention relates principally to the 10 discovery that the mechanical properties of molding resins comprising sorbent additives are capable of eliminating the usual requirement specifically for reinforcement additives, such as glass beads and glass fibers, some embodiments of the invention also contemplates multifunctional sorbent-resin molding compositions comprising moisture adsorbing-mechanical property enhancing amounts of adsorbent 15 in combination with reinforcing additives and resin, wherein reduced amounts of reinforcing additives can be employed than otherwise normally required for enhanced mechanical properties. That is, embodiments of the invention also provide desiccant containing molding compositions, but with reduced quantities of strength enhancing additives, such as glass fibers and glass beads. This may enhance the mechanical 20 properties of the molding composition without the potential for degrading the strength characteristics of the molded article. More specifically, proportional ranges of sorbent, reinforcing additives and resin can be from about 25 to about 50 Wt% sorbent; from about 5 to about 15 wt% reinforcing additive and from about 45 to about 70 wt% resin. 25 [0016] It has also been found as a part of embodiments of the present invention that, within limits, the resins can be processed and formed by several techniques, including modern high-speed injection molding processes into fully functional component parts, including parts for various sealed systems and assemblies. In these later applications, the structural and functional features of the 30 inventive concepts may be served while ambient and ingressed moisture are adsorbed to protect sensitive materials or components of systems or assemblies from degradation by moisture; e.g. hydrolysis or corrosion. 7 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ [0017] In accordance with the above, embodiments of the present invention comprises reinforced structural resin compositions suitable for injection molding with improved mechanical properties, satisfactory melt handling properties, and substantial moisture adsorption properties. Most thermoplastic resins are suitable for use in the 5 resin bonded adsorbent compositions of embodiment of the invention, and include homopolymers and copolymers comprising two or more monomers. Representative examples include the polyamides, such as Nylon 6; Nylon 6,6; Nylon 610, and so on. Other representative examples include the polyolefins, such as high and low density polyethylenes, polypropylene; copolymers of ethylene-vinyl acetate; polystyrene; 10 polyesters, e.g., PET, to name but a few. [0018] As previously discussed, according to one aspect of the invention, compositions of the present invention may comprise from about 25 to about 55 wt% sorbent and the balance resin, and more specifically, from about 25 to about 45 wt% sorbent with the balance resin. More preferred compositions may comprise from 15 about 35 to about 42 wt% sorbent, such as a molecular sieve, and the balance resin. A most preferred resin bonded sorbent composition may comprise from about 60% nylon molding resin, such as Zytel® 101, commercially available from E.I. duPont, compounded with 40% molecular sieve, such as W. R. Grace 4A molecular sieve powder. The molecular sieves of the invention can have a nominal pore size of 4 A, 20 and a particle size range of about 0.4 to about 32pi. It is to be noted, however, that other molecular sieve pore-sizes can be used as well, such as 3A, 5A, or 10X, for example. [0019] Generally, sorbents which are useful and functional in this invention are those which bond mechanically to the resin without special additives, such as 25 molecular sieve, as previously discussed. Still others, according to embodiments of the instant invention, can be induced to bond to the resin through use of a suitable additive, i.e., bind with the aid of a coupling or compatibilizing agent. In addition to molecular sieve, other representative sorbents that are useful in the compositions of the invention can include silica gel, activated carbon, activated alumina, clay, other 30 natural zeolites, and combinations thereof Those sorbents found to perform with coupling or compatibilizing agents can include such members as activated carbon and alumina. 8 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ [0020] The additives which perform as compatibilizers can fall into either of two categories, namely those which bond with the resin or the sorbent, and those having some affinity with both resin and sorbent, and act as solid state surfactants. Reactive coupling agents can include such classes as maleates, epoxies and silanes. 5 More specifically, reactive coupling agents can include such representative examples as maleic anhydride grafted polymers used in amounts ranging from about 2 to about 5 Wt%. In particular, they can include such representative examples as maleic anhydride grafted to polypropylene or ABS resins, the later being useful as coupling agents with styrenic polymers. Similarly, silanes with various functional groups 10 attached may be used. [0021] Embodiments of the present invention also contemplates the use of so called non-reactive type compatibilizing agents in binding sorbent and resin. This can comprises such representative examples as metals (e.g., zinc or sodium), acrylates, stearates and block copolymers, e.g., zinc stearate, sodium stearate in a range from 15 about 0.01 to about 0.02 wt% based of the sorbent. The actual level can be driven by the surface area, which is in-turn proportional to the particle size. For a molecular sieve with mean particle size of 10[t, 100 ppm of aluminum stearate can be a typical starting level for compatiblization with a polyamide resin. [0022] The resin bonded sorbent compositions may be prepared in accordance 20 with the present invention using plastic compounding techniques generally familiar among ordinary skilled artisans. Molecular sieve, a preferred sorbent, may be incorporated into the resin, e.g., polyamide, polyolefin, or the like, by feeding the sorbent in powdered format along with beads of the chosen resin to a plastics extruder with good mixing characteristics. A twin-screw extruder is typically used. Here, the 25 resin can be melted and the sorbent mixed throughout. It is a necessary condition that the melt blend be heated above the melt point of the resin as determined by DSC (differential scanning calorimetry). That is, in preparing the resin bonded sorbents of the invention, the temperature should be raised to the point where all crystallinity is lost in order to achieve complete miscibility of the sorbent in the resin melt. For 30 example, DuPont's Zytel® 101 polyamide resin would be heated above 262'C. The extruded resin is cooled and then cut or crushed into pellets or granules. Because compounding is performed at elevated temperatures, the sorbent tends not to adsorb 9 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ moisture during this processing period, but can retains its adsorption capacity when molded into a component part and installed in a working environment. [0023] One further advantage realized with the resin bonded sorbent system of the embodiments of the present invention, wherein the resin and sorbent are 5 intimately bonded, may be that gram for gram it is more effective than adsorbent systems employing a bagged adsorbent. According to earlier methods wherein bags were used for containerizing sorbent, the sorbent required beading to prevent it from entering the refrigerant stream, for example. This required the sorbent to be bonded within a binder resin, typically 15 wt% binder, such as in the form of a powder. Thus, 10 when 40 grams of a commercially prepared sorbent was placed into a bag, in reality only 34 grams of sorbent were introduced into the system (with 6 grams of binder). In contradistinction, the resin bonded sorbents of embodiments of the present invention require no additional binder resin because the sorbent is placed directly into the molding resin from which the components are fabricated. Advantageously, no 15 intermediary binder resin may be required, allowing for higher sorbent loading factors than otherwise achieved with the usual bagged sorbents. [0024] The compounded resin blend of embodiments of the invention, previously discussed, can then be injection molded in the form of a part. An exemplary part is a refrigerant vapor liquid separator, such as is used in the receiver of 20 an automotive air conditioning system. The strength of the silicate-reinforced resin can result in a structurally sound molded part. As such, it may be self-supporting and suitable for mounting in the same ways that metal or plastic refrigeration components are presently mounted. See, for example, Figs. 1 and 2, which show an end and partial cross sectional side view, respectively, of a U-Tube assembly 100. This 25 embodiment, which uses the composition of embodiments of the present invention to form a liner or sleeve 110 out of the resin bonded sorbent, contains a U-tube 120 within accumulator canister 130. This design can provide a means of drying against an exposed inner surface of liner 110. This embodiment is an alternative to a "baffle" type accumulator of the prior art (not shown). 30 [0025] Alternatively, the resin formed in accordance with embodiments of the present invention, instead of being melted and injection molded into a functional sorbent part, may be milled or otherwise formed or pelletized into pieces which are then sintered into parts, such as a flow-through monolith structure, or a flow-through 10 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ dryer component. In this case, the part is not injection molded, but can be molded from the compounded sorbent-loaded resin into a functional part having sufficient porosity for its intended application, such as for use in a receiver dryer assembly. [0026] Parts fabricated from the resin bonded sorbents of embodiments of the 5 present invention are particularly well suited to replace multiple-component parts of the prior art. For example, in the past many specialized structures have been developed to fit and secure a desiccant material (which was loose) in various parts of a refrigeration system. Welded or sewn bags containing beaded or granular molecular sieve or aluminum oxide would be disposed within a flow path. Additionally, and 10 specifically with respect to stationary refrigeration applications, beads or granules of desiccant were bonded together in a heated mold with a suitable heat-cured resin or ceramic binder to produce a rigid shape which would serve as a drying block or partial filter. Such a structure would be built into a housing. These solutions, however, involved complicated multiple part pieces. Embodiments of the present 15 invention, however, joins the performance of the desiccant with the structural purpose of a part such that a one-piece device serves both functions simultaneously. [0027] For example, embodiments of the present invention is contemplated for use with an Integrated Receiver Dehydrator Condenser, such as those which are starting to find their way into a growing number of vehicles. Such mobile 20 refrigeration cycle components basically combine the drying function with the condenser for a number of reasons. It reduces the number of system components, therefore making better use of under-hood space, and concomitantly reduces the number of fittings and connections minimizing the potential for system leaks. It also has some performance gains relative to cooling efficiencies. The current technology 25 is illustrated in Figs. 3 and 4 which show aluminum threaded plug 300 with O-rings 305 and 306, an injection molded filter 310, and desiccant bag 320. By converting this system to a one-piece injection molded plug/filter assembly, such as that shown in Fig. 5, a one piece plug 500 with O-ring 510 can be utilized. In such a case, plug 500 could be assembled with desiccant bag 600 as shown in Fig. 6. Fig. 7 illustrates a 30 partial cross section of the device assembled. [0028] More specifically, Fig. 7 shows the device 700 disposed adjacent condenser 710. Device 700 is comprised of desiccant bag 720 disposed within receiver dryer tube 730. On the end of device 700 is filter tube 740 housing integral 11 6073429_1 (GHMatters) P75921 .AU.1 ESTHERJ threaded plug and filter 750. O-rings 705 are also shown. Desiccant bag 720 is connected to integral threaded plug and filter 750 at interface 760. This design can eliminate all the separate assembly steps and create a part with fewer separate pieces, as compared to the aluminum threaded plug described above. 5 [0029] Still another embodiment incorporating the present invention is shown in Fig. 8, which illustrates a mobile refrigeration accumulator upper portion 800 of a refrigerant vapor/liquid separator, such as is used in the receiver of an automobile air conditioning system. As can be seen in Fig. 8, accumulator upper portion 800 contains J-Tube 810 which is mounted within it. In this case, one or both of these 10 pieces are molded from the resin bonded sorbent composition of the present invention. Fig. 9 illustrates cap 900 which would be placed over top accumulator upper portion 800. In a preferred embodiment of such an accumulator apparatus, both upper portion 800 and cap 900 would be injection molded and then welded, or possibly injection blow-molded in halves. Completing the device would be a lower portion (not shown) 15 which may also be molded from the resin bonded sorbent composition of the present invention. [0030] In order to demonstrate the benefits of the resin bonded sorbents of the present invention, the following experiments were performed: EXAMPLE 1 20 [0031] Embodiments of the invention will now be described with reference to the accompanying non-limiting examples. [0031a] Test samples of resin bonded sorbents were prepared according to the claimed invention employing the following protocols. The resins are procured from a supplier in pellet form (most common is cylindrical (.03-.12 inch diameter x .06-.25 25 inch long), other forms included tear drop format (.06-.19 inch). The ratio of molecular sieve to the resin is determined by weight of the components. The resin was premixed in a poly bag by hand (5-15 min). The pre-blend was emptied into the hopper of a Brabender single screw extruder. Action from the screw further blends and melts the resin and molecular sieve as it travels through the extruder barrel. The 30 resin bonded sorbent then exits through the single strand die (1 circular hole) at the end of the extruder forming one strand of molten material. The nylon based resin was heated above 262'C. The strand was then cooled by air. The strands were broken 12 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ into pieces. The pieces were placed in a hopper of an injection molding machine and parts molded. The parts were broken into pieces and re-introduced back into the injection molding machine where the tensile specimens (dog bones) were injection molded for testing. 5 [0032] The resin chosen was one known to be compatible with refrigerants used in modern air conditioning systems, specifically R-134a and R-152a. The resin was also compatible with compressor lubricants entrained in the refrigerant stream. The desiccant was the same as that most commonly used in conventional systems, namely a 3A or 4A molecular sieve. 10 [0033] For comparison, a commonly used reinforcing glass bead was compounded at about the same loading. Glass beads are added to a polymer melt to control shrinkage and to uniformly enhance mechanical properties. Glass beads were effective in this application because they bonded mechanically to the resin, so that after molding an isotropic structure resulted. 15 [0034] The compounded resin mechanical properties are compared with the pure polymer and with glass reinforced polymer in Table I. 13 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ Table I: Properties of Reinforced Nylon Molecular Glass Bead Material: Nylon Neat Sieve Reinforced Reinforced Nylon Property: Nylon Loading (%) 0 36.6 38.2 Hardness - Shore D 81.4 93 86.6 (ASTM D 2440) Tensile Modulus (psi) 203779 307252 361470 (ASTM D 638) Tensile Displacement @ Max Load (in.) 0.62 0.144 0.132 (ASTM D 638) Tensile Stress @ Max. Load (psi) 10907 10519 10412 (ASTM D 638) Flex Modulus (psi) 336577 3357439087 506988 (ASTM D 790) Flex Displacement @ Yield (in.) 0.531 0.142 0.156 (ASTM D 790) Flex Stress @ Yield (psi) 17114 16662 15132 (ASTM D 790) Heat Deflection Temp. (OF) 111.7 144.5 131.8 (ASTM D 648) [0035] When the resin was reinforced, the hardness increased and with it the tensile displacement and flex displacement decreased dramatically as the material 5 became more metal-like. Accordingly, the tensile and flex modulus were increased significantly. With glass and sorbent reinforced nylon (without glass reinforcement), 14 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ the tensile and flex stress was substantially maintained. The important feature and the significance of this finding was that the properties of the sorbent reinforced nylon vary from pure nylon in the same way as does glass reinforced nylon, both in direction and magnitude. In addition, the heat deflection temperature was increased. 5 Heat deflection temperature is a measure of heat resistance. This term is known among those skilled in the art. It is an indicator of the ability of the material to withstand deformation from heat over time. A further implication of the increased heat deflection temperature was an increase in the service temperature of a part molded from the sorbent reinforced resin. 10 [0036] It was also found that structures molded from sorbent reinforced nylon resin (without glass reinforcement) are isotropic as evidenced by the fact that tensile and flex modulus were substantially the same in one direction as another. As further evidence, shrinkage out of a mold is minimal and symmetrical. 15 EXAMPLE 2 [0037] Further experiments were performed using compositions comprising polypropylene, namely Huntsman Polypropylene 6106. This resin was also compatible with refrigerants, as well as with compressor lubricant. It was compounded in a similar fashion as nylon in Example 1, namely: 60% polypropylene 20 resin and 4 0% molecular sieve Type 4A. The resin was heated above 174'C. The compounded resin had similar advantageous mechanical properties compared to the pure resin, and performs, structurally, close to that of a glass reinforced resin. Its properties are summarized in Table II. The values were determined by the same ASTM standards as provided in Table I. 25 15 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ Table 11: Properties of Reinforced Polypropylene Molecular Sieve Glass Bead Glass Fiber Material: PP Neat Reinforced Reinforced Reinforced Property: Polypropylene Polypropylene Polypropylene Loading (%) 0 37.5 41.9 39.4 Hardness - Shore D 66.8 74.6 65.6 75.4 Tensile Modulus (psi) 131242 228023 159321 342977 Tensile Displacement 0.330 0.137 0.274 0.222 @ Max Load (in.) Tensile Stress @ 3583 3169 2188 15996 Max. Load (psi) Flex Modulus (psi) 113251 219377 158136 737113 Flex Displacement @ 0.597 0.356 0.468 0.176 Yield (in.) Flex Stress @ Yield 14.368 14.298 9.781 60.7 (psi) Heat Deflection 121.3 145.1 128.8 n/a Temp. ('F) [0038] Reinforcement of polypropylene resulted in increased hardness and increases in tensile and flex modulus. For each of these properties the sorbent alone 5 demonstrated even greater reinforcement effect than glass bead reinforcement. Accordingly, tensile displacement and flex displacement were reduced as the material became more rigid. Again, the effect of the sorbent was directionally the same as, but greater than glass bead reinforcement. Tensile and flex stress were reduced only slightly with sorbent reinforcement. However, the reduction was greater with glass 10 reinforcement. With polypropylene, the reinforcement with sorbent was generally more effective than with glass bead reinforcement. The heat deflection temperature was increased. Here again, a further implication of the increased heat deflection temperature was an increase in the service temperature of a part molded from the sorbent reinforced resin. 16 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ [0039] Similarly, it was further found that structures molded from sorbent reinforced polypropylene resin were isotropic as evidenced by the fact that tensile and flex modulus were substantially the same in one direction, as another. As further evidence, shrinkage out of a mold was minimal and symmetrical. 5 EXAMPLE 3 [0040] As may be seen in Table III, melt flow was reduced with sorbent reinforced nylon compared with nylon neat (pure polymer) or glass bead reinforced nylon. Nevertheless it was in a workable range and was higher than polypropylene. 10 Melt flow of sorbent reinforced polypropylene was improved relative to polypropylene neat or glass reinforced polypropylene. Table III: Melt Flow Properties of Sorbent Reinforced Polymers Melt Flow Index (g/10 min) Neat Molecular Sieve Glass Bead Reinforced Reinforced (ASTM D 1238) Nylon 56.3 14.7 55.5 Polypropylene 5.3 7.3 2.1 15 EXAMPLE 4 [0041] Moisture adsorption as a percentage of part weight is significant. This may be seen in Table IV. In practice, molecular sieve will adsorb about 25% of its own weight. It is reasonable then to expect a 40% loaded polymer to adsorb 10% of its own weight. In the case of nylon, however, adsorption reaches 13%. This was 20 presumably the result of the action of the sorbent coupled with adsorption of some water by the nylon itself. The fact that the body as a whole adsorbs in excess of 10% indicates that the sorbent in addition to reinforcing the nylon was fully functional as a sorbent even though dispersed in the polymer. There was, in effect, a synergistic 17 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ effect, or a double duty by the sorbent. Table IV shows results of adsorption at 36 38% molecular sieve loading. Table IV: Adsorption Properties of Sorbent Reinforced Polymers Moisture Adsorption @ 2 Days 10 days 23 days 38 Days 29'C, 90% r.h. Molecular Sieve 5.4% 12.4% 13% 13% Reinforced Nylon Molecular Sieve Reinforced 1.1% 2.8% 4.4% 5.7% Polypropylene 5 [0042] Polypropylene is hydrophobic and is thus much slower to adsorb moisture. But it is fully functional as a sorbent while being fully functional as a molding resin. [0043] Additional applications of this invention are numerous. Such applications would include any resin bonded component or structure used in an air 10 conditioning or refrigeration system. As discussed above, examples include J-tubes that are injection molded in halves and welded or possibly injection blow-molded, sleeve liners, coatings for an interior part or shell, co-injection molded composite structures, and insert molded filter-dryer assemblies. Diagnostic applications would include test strip substrates, case or supports for E-trans cases, containers or 15 components of containers for diagnostic products. Pharmaceutical applications would include parts of a tablet container, such as a base, or closure, or the body of the container itself, an insert into a tablet container such as a bottom support or a neck insert to aid in dispensing, a thermoformed sheet or as a layer of a multilayer thermoformable sheet suitable for one-at-a-time or two-at-a-time dose dispensing 20 from a blister or other compartmented package. Electronics and electro-optical device applications would include complete breather filter bodies, inserts for night vision sensor units, or inserts for rear view camera bodies. [0044] It will be appreciated that there are many other potential applications for a desiccant loaded injection moldable resin in closed systems and sealed 18 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ packaging applications. It must also be appreciated that a desiccant loaded injection molding resin can also be extruded into a rod or channel or any other shape with a uniform cross-section because extrusion is a less demanding process than injection molding. 5 [0045] Although the present invention has been particularly described in conjunction with specific preferred embodiments, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art. It is therefore contemplated that the appended claims will embrace any such alternatives, modifications, and variations as falling within the true scope and spirit of the present 10 invention. [0046] It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country. [0047] In the claims which follow and in the preceding description of the 15 invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention. 20 19 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ

Claims (15)

1. A molded article formed of a composition comprising from 25 to 55 wt% of a molecular sieve in combination with from 45 to 75 wt% of a thermoplastic resin comprising nylon, wherein said molecular sieve-nylon combination is present in said 5 composition as a nylon bonded molecular sieve, said molecular sieve comprising a plurality of particles mixed throughout said nylon in a miscible manner
2. The article according to claim 1, wherein said composition does not comprise 10 a coupling agent or a compatibilizing agent to promote bonding of said nylon and said molecular sieve.
3. The article according to claims 1, wherein said composition comprises a coupling agent or a compatibilizing agent to promote bonding of said nylon and said 15 molecular sieve.
4. The article according to Claim 3, wherein said coupling or compatibilizing agent is a member selected from the group consisting of reactive and nonreactive agents. 20
5. The article according to Claim 4, wherein said reactive agent and non-reactive agent is a member selected from the group consisting of a metal, an acrylate, stearate, block copolymer, maleate, epoxy and a silane. 25
6. The article according to any preceding claim, wherein said nylon bonded molecular sieve comprises from 35 to 42 wt% molecular sieve and from 58 to 65 wt% thermoplastic nylon.
7. The article according to any preceding claim, wherein said composition does 30 not comprise any reinforcing additive other than said molecular sieve.
8. The article according to any one of claims 1 to 7, wherein said composition comprises from 5 to 15% of a reinforcing agent in addition to said sorbent. 35
9. The article according to any preceding claim, wherein said article is a refrigeration or air conditioning cycle component. 20 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ
10. The article according to claim 9, wherein said component is a member selected from the group consisting of a U-tube assembly; a liner or sleeve; accumulator, plug/filter assembly; integral threaded plug and filter, and accumulator-J-tube and cap. 5
11. The article according to any preceding claim, wherein said article is an injection molded article.
12 A method of manufacturing an article according to any preceding claim, 10 comprising of steps of: (i) providing a molding composition comprising from 25 to 55 wt% of a molecular sieve in combination from 45 to 75 wt% of a thermoplastic resin comprising nylon wherein said molecular sieve-nylon combination is present in said composition as a nylon bonded molecular sieve, said molecular sieve comprising a plurality of 15 particles mixed throughout said nylon in a miscible manner, and (ii) molding said component from said article.
13 A method according to claim 12, wherein said step of molding is injection molding. 20
14. A molded article substantially as herein described with reference to the accompanying drawings and/or the examples.
15. A method of manufacturing an article substantially as herein described with 25 reference to the accompanying drawings and/or the examples. 21 6073429_1 (GHMatters) P75921.AU.1 ESTHERJ
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Citations (5)

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US4013566A (en) * 1975-04-07 1977-03-22 Adsorbex, Incorporated Flexible desiccant body
EP0400460A1 (en) * 1989-05-23 1990-12-05 Sasaki Chemicals Co., Ltd. Moisture-absorbent compositions
US5114584A (en) * 1990-12-13 1992-05-19 Refractron Technologies Corporation Filter dryer body
US5432214A (en) * 1992-11-20 1995-07-11 Airsec Industries, Societe Anonyme Polymer-based dehydrating materials
US6059860A (en) * 1996-06-21 2000-05-09 3M Innovative Properties Company Sorptive articles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013566A (en) * 1975-04-07 1977-03-22 Adsorbex, Incorporated Flexible desiccant body
EP0400460A1 (en) * 1989-05-23 1990-12-05 Sasaki Chemicals Co., Ltd. Moisture-absorbent compositions
US5114584A (en) * 1990-12-13 1992-05-19 Refractron Technologies Corporation Filter dryer body
US5432214A (en) * 1992-11-20 1995-07-11 Airsec Industries, Societe Anonyme Polymer-based dehydrating materials
US6059860A (en) * 1996-06-21 2000-05-09 3M Innovative Properties Company Sorptive articles

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